US5473010A - Polyimide based resin composition - Google Patents

Polyimide based resin composition Download PDF

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US5473010A
US5473010A US08/297,854 US29785494A US5473010A US 5473010 A US5473010 A US 5473010A US 29785494 A US29785494 A US 29785494A US 5473010 A US5473010 A US 5473010A
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parts
polyimide
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Atsushi Morita
Tomohito Koba
Toshiaki Takahashi
Katsunori Shimamura
Toshiyuki Kataoka
Hiroyuki Furukawa
Hiroaki Tomimoto
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Mitsui Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a heat resistant polyimide based resin composition having excellent resistance to fatigue and creep, and more particularly relates to a polyimide based resin composition comprising polyaryl ether ketone and polyetherimide in addition to extremely heat resistant polyimide and having improved fatigue resistance.
  • polyimides which have been conventionally developed exhibit excellent properties such as heat resistance, static mechanical properties and chemical resistance.
  • conventional polyimides have been insufficient in permanence properties such as fatigue resistance and creep properties.
  • a polyetherimide having recurring structural units of the formula (A): ##STR1## has a relatively high glass transition temperature of 210° ⁇ 220° C. and good static mechanical strength and has been developed its uses in various fields.
  • the polyimide is deficient in durability such as resistance to fatigue and creep, and thus it has been difficult to develop uses for parts which require durability, that is, components which are exposed to repeated high stress.
  • the polyimide has a glass transition temperature which is 30° ⁇ 40° C. higher than that of the polyetherimide of the formula (A) and is excellent in mechanical properties. In point of permanence properties such as fatigue resistance and creep properties, the polyimide is considerably improved as compared with the polyetherimide having recurring structural units of the formula (A). However, the improvement has been still unsatisfactory.
  • polyimides having various outstanding properties for example, a trial of alloying the polyimide having recurring structural units of the above formula (B) with polyarylether ketone having good durability has been proposed. However, a sufficiently improved polymer alloy has not yet been provided.
  • An object of the present invention is to provide a polyimide based resin composition having good resistance to fatigue and creep.
  • a polyimide based resin composition having good resistance to fatigue and creep can be obtained by mixing polyimide having recurring structural units of the below described formula (1) and polyarylether ketone with polyetherimide in a specific range of composition, and alloying the resultant mixture.
  • the present invention has been completed.
  • a polyimide based resin composition comprising 1 ⁇ 50 parts by weight of polyetherimide for 100 parts by weight of a resin composition comprised of 50 ⁇ 5 parts by weight of polyarylether ketone and 50 ⁇ 95 parts by weight of a polyimide having recurring structural units represented by the formula (2): ##STR5## wherein X is one or more radicals selected from the group consisting of a direct bond, divalent hydrocarbon radical having 1 ⁇ 10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio, sulfonyl and ether radical, and Y 1 , Y 2 , Y 3 and Y 4 are individually one or more radicals selected from the group consisting of a hydrogen atom, lower alkyl radical, lower alkoxy radical, chlorine atom and bromine atom; and R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4 ⁇ 9 carbon
  • a polyimide based resin composition comprising 1 ⁇ 50 parts by weight of polyetherimide for 100 parts by weight of a resin composition comprised of 50 ⁇ 1 parts by weight of polyarylether ketone and 50 ⁇ 99 parts by weight of a polyimide having recurring structural units represented by the formula (3): ##STR6##
  • R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4 ⁇ 9 carbon atoms, monocyclic aliphatic radical having 4 ⁇ 10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member,
  • polyimide based resin composition wherein the polyimide comprises an end-capped polyimide polymer obtained by reacting diamine compound and tetracarboxylic dianhydride in the presence of aromatic dicarboxylic anhydride of the formula (4): ##STR7## wherein Z is a divalent radical having 6 ⁇ 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, and/or aromatic monoamine represented by the formula (5):
  • V is a monovalent radical having 6 ⁇ 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member,
  • a polyimide based resin composition which comprises 5 to 65 parts by weight of fibrous reinforcements for 100 parts by weight of the above polyimide based resin compositions, and
  • the polyimide based resin composition of the present invention has excellent fatigue resistance, creep properties, and mechanical strength at a high temperature, and can be widely applied in the fields for parts which these characteristics is desired, for example, machine parts such as gears, shaft bushes, cams, bushings pulleys and sleeves; automobile parts such as impellers, manifolds, valve lifters, piston skirts, oil pans; and front covers, and chains.
  • Polyimide used in the polyimide based resin composition of the present invention comprises one or more recurring structural units represented by the formula (1): ##STR10## wherein Ar and R are the same as above.
  • Exemplified polyimides include polyimide having recurring structural units represented by the formula (3): ##STR11## wherein R is the same as above, which Ar in the formula (1) is ##STR12## or polyimide having recurring structural units represented by the formula (2): ##STR13## wherein X, Y 1 ⁇ Y 4 and R are the same as above, which Ar in the formula (1) is ##STR14## wherein X and Y 1 ⁇ Y 4 are the same as above.
  • the polyimide used in the present invention can be prepared by the following processes.
  • Aromatic diamine compounds used as raw materials for the polyimide having recurring structural units represented by the formula (1) as fundamental skeleton are aromatic diamino compounds represented by the formula (1-1) ##STR15## that is, the aromatic diamine compounds are 1,3-bis(3-aminophenoxy)benzene represented by the formula (3-1): ##STR16## as a raw material for the polyimide having recurring structural units represented by the formula (3), and aromatic diamine compounds represented by the formula ( 2-1 ): ##STR17## wherein X is one or more radicals selected from the group consisting of a direct bond, divalent hydrocarbon radical having 1 ⁇ 10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio, sulfonyl and ether radical, and Y 1 , Y 2 , Y 3 and Y 4 are individually one or more radicals selected from the group consisting of a hydrogen atom, lower alkyl radical, lower alkoxy radical, chlorine atom and
  • the polyimide used in the present invention can be prepared by reacting one or more aromatic diamines with one or more tetracarboxylic dianhydrides represented by the formula (12): ##STR18## wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4 ⁇ 9 carbon atoms, monocyclic aliphatic radical having 4 ⁇ 10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, in a solvent and then thermally or chemically imidizing the resultant polyamic acid.
  • R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4 ⁇ 9 carbon atoms, monocyclic aliphatic radical having 4 ⁇ 10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, in
  • Exemplary diamine compounds represented by the above formula (2-1) include;
  • diamine compounds may be used either singly or in combination of two or more.
  • the polyimide used in the present invention is prepared by using the above aromatic diamine compound as raw materials.
  • the polyimide prepared by simultaneous use of other diamines can also be used for the composition of the invention as long as no adverse effect is found on the good melt-flowability of the polyimide.
  • diamines which may be used as a mixture include, for example, m-aminobenzylamine, p-aminobenzylamine, bis(3-aminophenyl)ether, (3-aminophenyl)(4-aminophenyl)ether, bis(4-aminophenyl)ether, bis(3-aminophenyl)sulfide, (3-aminophenyl)(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis(3-aminophenyl)sulfone, (3-aminophenyl)(4-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)
  • aromatic diamine compounds are usually used with amount of less than 30% by weight per the essential aromatic diamine compound, preferably less than 5% by weight.
  • Tetracarboxylic dianhydride which is another raw material for preparing the polyimide used in the present invention is represented by the above formula (12).
  • R is one or more tetravalent radicals selected from the group consisting of from (a) to (e):
  • Tetracarboxylic dianhydrides for preparing the polyimide used in the present invention include, for example,
  • R of the formula (12) is the following formula; ##STR24## and (1) wherein X 1 in the above formula is direct bond; for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride,
  • X 1 in the above formula is ether radical, for example, bis(3,4-dicarboxyphenyl)ether dianhydride;
  • X 1 in the above formula is thio radical, for example, bis(3,4-dicarboxyphenyl)thioether dianhydride;
  • X 1 in the above formula is an aliphatic radical such as --CH 2 --, --C(CH 3 ) 2 -- and --C(CF 3 ) 2 --, for example,
  • X 1 of the above formula is a sulfonyl radical, for example,
  • tetracarboxylic dianhydrides may be used either singly or in combination of two or more.
  • the capped polyimide having at the polymer chain end an aromatic ring which is unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride, or the polyimide containing the end-capped polyimide, also may be used in the polyimide based resin composition of the present invention.
  • the end-capped polyimide can be prepared by reacting the above diamine compound with the above tetracarboxylic dianhydride in the presence of aromatic dicarboxylic anhydride of the formula (4): ##STR25## wherein Z is a divalent radical having 6 ⁇ 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, and/or aromatic monoamine represented by the formula (5):
  • V is a monovalent radical having 6 ⁇ 15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
  • Exemplary aromatic dicarboxylic anhydrides of the formula (4) include phthalic anhydride, 2,3-benzophenonedicarboxylic anhydride, 3,4-benzophenonedicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,
  • Phthalic anhydride is most preferred in view of properties and utility of polyimide obtained.
  • the amount of aromatic dicarboxylic anhydride used is 0.001 ⁇ 1.0 mol per mol of the above aromatic diamine represented by the formula (2-1) or (3-1). An amount less than 0.001 mol leads to viscosity increase in processing at high temperatures and causes deterioration of processability. On the other hand, an amount exceeding 1.0 mol results in lowered mechanical properties. Preferred amount is in the range of 0.01 to 0.5 mol.
  • Aromatic monoamines of the formula (5) include, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehy
  • the amount of aromatic monoamine is 0.001 ⁇ 1.0 mol per mol of the aromatic tetracarboxylic dianhydride represented by the above formula (12).
  • An amount less than 0.001 mol leads to a viscosity increase in processing at high temperatures and causes deterioration of processability. On the other hand, an amount exceeding 1.0 mol results in lowered mechanical properties. Preferred amount is in the range of 0.01 ⁇ 0.5 mol.
  • Polyimide used in the present invention can be prepared by any known process. For example, preparation is carried out by the following processes.
  • a process for preparing polyamic acid in an organic solvent isolating the polyamic acid by removing the solvent at a low temperature under reduced pressure or by pouring the resulting polyamic acid solution into a lean solvent, and imidizing the polyamic acid by heating to obtain polyimide.
  • Organic solvents which can be used include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-ch
  • the reaction temperature for polymerization and imidization is 300° C. or less.
  • No particular limitation is imposed upon the reaction pressure, and the reaction can be sufficiently carried out under atmospheric pressure.
  • the reaction time differs depending upon diamine, tetracarboxylic dianhydride, solvent, catalyst and reaction temperature.
  • the reaction time of 4 ⁇ 24 hours is usually sufficient.
  • Polyimide having recurring structural units represented by the formula (1) used in the present invention usually has an inherent viscosity of 0.35 ⁇ 1.0 dl/g, preferably 0.40 ⁇ 0.95 dl/g, more preferably 0.4 ⁇ 0.9 dl/g.
  • inherent viscosity 0.35 ⁇ 1.0 dl/g, preferably 0.40 ⁇ 0.95 dl/g, more preferably 0.4 ⁇ 0.9 dl/g.
  • the inherent viscosity is less than 0.35 dl/g, mechanical strengths and durability of polyimide itself are insufficient.
  • an inherent viscosity exceeding 1.0 dl/g injection molding is very difficult because of poor processability.
  • Inherent viscosity was measured at 35° C. after heat-dissolving polyimide in a solvent mixture composed of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol at a concentration of 0.5 g/100 ml.
  • Polyarylether ketone used in the polyimide based resin composition of the present invention includes a polyarylether ketone which comprises at least one selected from the group consisting of structural units represented by the formulae of from (6) to (10): ##STR26##
  • the polyarylether ketone may be a homopolymer having one of structural unit selected from formulae (6) ⁇ (10), or may be a copolymer having two or more of structural units selected from formulae (6) ⁇ (10), or may be mixture comprising these homopolymers and/or copolymers.
  • composition for polyarylether ketone and polyimide in the polyimide based resin composition comprises 50 to 1 parts by weight of polyarylether ketone and 50 to 99 parts by weight of polyimide having recurring structural units represented by the formula (1).
  • the composition comprising the polyimide having recurri-structural units of the formula (2), especially, the composition comprises 50 to 5 parts by weight of polyarylether ketone and 50 to 95 parts by weight of the polyimide.
  • the composition preferably comprises 50 to 1 parts by weight of polyarylether ketone and 50 to 99 parts by weight of the polyimide.
  • an amount exceeding 50 parts by weight of the polyarylether ketone also tends to lower heat resistance of the polyimide, and an amount less than 1 parts by weight is insufficient to improve permanence properties.
  • Polyetherimide used in the polyimide based resin composition of the present invention has a recurring structural units represented by the following formula: ##STR27## wherein D is a trifunctional aromatic group where two functional groups out of three are connected with adjacent carbon atoms, both E and Ar 1 are residue of divalent aromatic group.
  • the polyetherimide is a polymer consisting of ether and imide linkages as a required bonding unit and is substantially composed of recurring units which are represented by the above formula.
  • Exemplary structural units of the polyetherimide are as follows; ##STR28## and E in these formula is residue of divalent aromatic group such as, ##STR29##
  • polyetherimide represented by the formula (11) ##STR30## is preferably used in the present invention.
  • the polyetherimide is commercially available from General Electric Co. with the Trade Mark of ULTEM-1000.
  • An amount of polyetherimide in the polyimide based resin composition is 1 to 50 parts by weight for 100 parts by weight of a resin composition comprising 50 to 99 parts by weight of polyimide used in the present invention, that is, the polyimide represented by the formula (1), (2) or (3), and 50 to 1 parts by weight of polyarylether ketone, preferably 5 to 25 parts by weight, more preferably 10 to 20 parts by weight.
  • the polyimide based resin composition has also achieved a marked improvement on high temperature durability in addition to the improvement of permanence properties at room temperature. Thus good durability can also be maintained at high temperature.
  • the present resin composition can exhibit outstandingly improved mechanical strength, especially permanence properties, by heat treating the composition at the specified temperature.
  • the temperature for the heat-treatment is the range of from 150° to 370° C., preferably from 160° to 330° C., more preferably from 160° to 320° C.
  • Times for heat treatment varies depending upon treating temperature, usually, the time is at least 4 hours in the above temperature range.
  • the polyimide based resin composition of the present invention includes another polyimide based resin composition reinforced by a fibrous reinforcement, which is comprised of the polyimide, the polyarylether ketone, the polyetherimide and a fibrous reinforcement.
  • Exemplary fibrous reinforcements which can be used in this composition include glass fibers, ceramic fibers, potassium titanate fibers, aromatic polyamide fibers, metal fibers, boron fibers, silicon carbide fibers, asbestos fibers, rock fibers and carbon fibers, preferably, glass fibers, aromatic polyamide fibers, potassium titanate fibers and carbon fibers.
  • the amount of the fibrous reinforcements used in the polyimide based resin composition is 5 ⁇ 65 parts by weight for 100 parts by weight of the above resin composition comprised of the polyimide, the polyarylether ketone and the polyetherimide, preferably 10 ⁇ 60 parts by weight.
  • the polyimide based resin composition having excellent fatigue characteristics can be obtained by adding the fibrous reinforcements in the amount of the above range to the above resin composition.
  • one or more additives can be added, if desired.
  • Exemplary additives which can be used include, fillers such as calcium carbonate, mica, glass beads, graphite, molybdenum disulfide, clay, silica, alumina, talc, diatomaceous earth, hydration alumina and shirasu balloons; lubricants; release agents; stabilizers; colorants; crystalline nucleating agents; plasticizer; other noncrystalline resins such as polyether sulfone, polyether imide, polysulfone and polycarbonate; other crystalline resins such as polyphenylene sulfide, polyether nitrile, polyamide and polyamideimide, and thermosetting resins such as epoxy resin, silicone resin and polyamide imide resin.
  • fillers such as calcium carbonate, mica, glass beads, graphite, molybdenum disulfide, clay, silica, alumina, talc, diatomaceous earth, hydration alumina and shirasu balloons
  • lubricants such as calcium carbonate
  • the polyimide based resin composition of the present invention can provide various forms of articles, which have good resistance to fatigue and creep, by changing the mold for injection molding.
  • the articles by injection molding can be applied of the field in parts such as machine parts and automobile parts, wherein the noted characteristics are required.
  • composition obtained in each example and comparative example were tested by the following methods.
  • the polyarylether ketones used in the examples and comparative examples have individually the following structural units.
  • polyimide which was prepared from 4,4'-bis(3-aminophenoxy)biphenyl and pyromellitic dianhydride and had an inherent viscosity of 0.50 dl/g and 10 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of General Electric Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370° ⁇ 400° C. and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 900 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in examples 2 ⁇ 10 in Table 1 were used.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in examples 11 and 12 in Table 1 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone ketone, were used.
  • PEKEKK ULTRA PEK A 1000; Trade Mark of B.A.S.F.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in example 13 in Table 1 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
  • PEK PEK 220; Trade Mark of I.C.I. Ltd.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 1 in Table 2 were used.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 2 in Table 2 and PEEK (PEEK 450 P; Trade Mark of I.C.I.Ltd.) as polyarylether ketone, were used.
  • PEEK PEEK 450 P; Trade Mark of I.C.I.Ltd.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 3 in Table 2 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, were used.
  • PEKEKK ULTRA PEK A 1000; Trade Mark of B.A.S.F.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 4 in Table 2 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
  • PEK PEK 220; Trade Mark of I.C.I. Ltd.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 5 in Table 2 and PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
  • PEEK PEEK 450 P; Trade Mark of I.C.I. Ltd.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 6 in Table 2 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, were used.
  • PEKEKK ULTRA PEK A 1000; Trade Mark of B.A.S.F.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 7 in Table 2 and PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
  • PEEK PEEK 450 P; Trade Mark of I.C.I. Ltd.
  • Test specimens were prepared by carrying out the same procedures as described in Example 1 except that PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
  • PEEK PEEK 450 P; Trade Mark of I.C.I. Ltd.
  • polyimide which was prepared from 4,4'-bis(3-aminophenoxy)biphenyl and pyromellitic dianhydride and had an inherent viscosity of 0.50 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370° ⁇ 420° C. While charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Test specimens were prepared by carrying out the same procedures as described in Example 14 except that resin composition and carbon fiber illustrated in examples 15 ⁇ 18 in Table 3, were used.
  • Test specimens were prepared by carrying out the same procedures as described in Example 14 except that resin and carbon fiber illustrated in comparative examples 9 and 10 in Table 3, were used.
  • polyimide which was prepared from 4,4'-bis(3-aminophenoxy)biphenyl and pyromellitic dianhydride and had an inherent viscosity of 0.50 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 15 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370° ⁇ 420° C. while charging from a side feeder 5 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Test specimens were prepared by carrying out the same procedures as described in Example 19 except that carbon fiber illustrated in examples 20 ⁇ 23 in Table 4, were used.
  • polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 20 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370° ⁇ 400° C. and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 900 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Test specimens were prepared by carrying out the same procedures as described in Example 24 except that compositions illustrated in comparative example 25 ⁇ 32 in Table 5, were used.
  • Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in example 33 in Table 6 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, were used.
  • PEKEKK ULTRA PEK A 1000; Trade Mark of B.A.S.F.
  • Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in example 33 in Table 6 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
  • PEK PEK 220; Trade Mark of I.C.I. Ltd.
  • Test specimens obtained in Example 34 were heat-treated for 4 hours at 220° C.
  • polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of aniline as end-capping agent and had an inherent viscosity of 0.65 dl/g and 40 parts by weight of polyarylether ketone (PEKEKK) (ULTAR PEK A-1000; Trade Mark of B.A.S.F.), 10 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twice screw extruder at 370° ⁇ 400° C. and cut in to pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 900 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • PEKEKK polyarylether ketone
  • Test specimens obtained in Example 36 were heat-treated for 4 hours at 220° C.
  • Polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end capping agent and had an inherent viscosity of 0.65 dl/g extruded through a twin screw extruder at 370° ⁇ 400° C. and cut into pellets.
  • the pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 900 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in comparative examples 12 ⁇ 15 in Table 7 and PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, are used.
  • PEEK PEEK 450 P; Trade Mark of I.C.I. Ltd.
  • Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in comparative example 16 in Table 7 and PEKEKK (ULTRA PEK A-1000; Trade Mark of B.A.S.F.) as polyarylether ketone, are used.
  • PEKEKK ULTRA PEK A-1000; Trade Mark of B.A.S.F.
  • Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in comparative example 17 in Table 7 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, are used.
  • PEK PEK 220; Trade Mark of I.C.I. Ltd.
  • Polyarylketone (PEEK 450 P; Trade mark; I.C.I. Ltd.) extruded through a twice screw extruder at 370° ⁇ 400° C. and cut into pellets.
  • the pellets thus obtained were injection molded at cylinder temperature of 360° ⁇ 380° C., injection pressure of 900 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I.Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370° ⁇ 420° C. While charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Composition of examples 39 ⁇ 40 illustrated in Table 8 was dryblended respectively and successively extruded through a twin screw extruder at 370° ⁇ 420° C. while charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets.
  • the pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 20 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 15 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370° ⁇ 420° C. while charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • test specimens obtained above were heat-treated for 4 hours at 220° C.
  • Test specimens were prepared by carrying out the same procedures as described in Example 41 except that composition illustrated in example 42 in Table 8 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, are used.
  • PEK PEK 220; Trade Mark of I.C.I. Ltd.
  • Test specimens were prepared by carrying out the same procedures as described in Example 41 except that composition illustrated in example 43 in Table 8 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, are used.
  • PEKEKK ULTRA PEK A 1000; Trade Mark of B.A.S.F.
  • Test specimens obtained in Example 38 were heat-treated for 4 hours at 220° C.
  • Polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g extruded through a twin screw extruder at 370° ⁇ 420° C. while charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets.
  • the pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Test specimens obtained in comparative example 19 were heat-treated for 4 hours at 220° C.
  • Polyarylether ketone (PEEK 450 CF 30 weight % pellet; Trade mark: I.C.I. Ltd.) were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 180° C. to form test specimens.
  • polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 15 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370° ⁇ 420° C. while charging from a side feeder 5 parts by weight of carbon fibers for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370° ⁇ 410° C., injection pressure of 2300 kg/cm 2 and mold temperature of 160° C. to form test specimens.
  • Test specimens were prepared by carrying out the same procedures as described in Example 45 except that carbon fibers illustrated in examples 46 ⁇ 49 in Table 10, were used.

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Abstract

The present invention relates to a polyimide based resin composition comprises 1 to 50 parts by weight of polyetherimide for 100 parts by weight a resin composition comprising 50 to 99 parts by weight of polyarylether ketone and 50 to 1 parts by weight of polyimide having specific structural units.
The polyimide based resin compositions have excellent fatigue characteristics and creep resistance and are expected widely to apply in field of machine and automobile parts which is required permanence for mechanical strength.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a heat resistant polyimide based resin composition having excellent resistance to fatigue and creep, and more particularly relates to a polyimide based resin composition comprising polyaryl ether ketone and polyetherimide in addition to extremely heat resistant polyimide and having improved fatigue resistance.
2. Description of the Related Art
Many kinds of polyimides which have been conventionally developed exhibit excellent properties such as heat resistance, static mechanical properties and chemical resistance. However, conventional polyimides have been insufficient in permanence properties such as fatigue resistance and creep properties. For example, a polyetherimide having recurring structural units of the formula (A): ##STR1## has a relatively high glass transition temperature of 210°˜220° C. and good static mechanical strength and has been developed its uses in various fields.
The polyimide, however, is deficient in durability such as resistance to fatigue and creep, and thus it has been difficult to develop uses for parts which require durability, that is, components which are exposed to repeated high stress.
In order to solve these problems, polyimide having recurring structural units represented by the formula (B): ##STR2## has already been developed (Japanese Laid Open Patent SHO 62-236858 and 62-253655).
The polyimide has a glass transition temperature which is 30°˜40° C. higher than that of the polyetherimide of the formula (A) and is excellent in mechanical properties. In point of permanence properties such as fatigue resistance and creep properties, the polyimide is considerably improved as compared with the polyetherimide having recurring structural units of the formula (A). However, the improvement has been still unsatisfactory.
For the demand of a polyimide having excellent durability, polyimides having various outstanding properties, for example, a trial of alloying the polyimide having recurring structural units of the above formula (B) with polyarylether ketone having good durability has been proposed. However, a sufficiently improved polymer alloy has not yet been provided.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a polyimide based resin composition having good resistance to fatigue and creep.
As a result of an intensive investigation in order to accomplish the object, the present inventors have found that a polyimide based resin composition having good resistance to fatigue and creep can be obtained by mixing polyimide having recurring structural units of the below described formula (1) and polyarylether ketone with polyetherimide in a specific range of composition, and alloying the resultant mixture. Thus, the present invention has been completed.
That is, one aspect of the present invention is a polyimide based resin composition having good resistance to fatigue and creep, comprising 1˜50 parts by weight of polyetherimide for 100 parts by weight of a resin composition comprised of 50˜1 parts by weight of polyarylether ketone and 50˜99 parts by weight of a polyimide having recurring structural units represented by the formula (1): ##STR3## wherein Ar is ##STR4## wherein X is one or more radicals selected from the group consisting of a direct bond, divalent hydrocarbon radical having 1˜10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio, sulfonyl and ether radical, and Y1, Y2, Y3 and Y4 are individually one or more radicals selected from the group consisting of a hydrogen atom, lower alkyl radical, lower alkoxy radical, chlorine atom and bromine atom; and R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4˜9 carbon atoms, monocyclic aliphatic radical having 4˜10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
Other aspects of the present invention are preferably, (1) a polyimide based resin composition comprising 1˜50 parts by weight of polyetherimide for 100 parts by weight of a resin composition comprised of 50˜5 parts by weight of polyarylether ketone and 50˜95 parts by weight of a polyimide having recurring structural units represented by the formula (2): ##STR5## wherein X is one or more radicals selected from the group consisting of a direct bond, divalent hydrocarbon radical having 1˜10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio, sulfonyl and ether radical, and Y1, Y2, Y3 and Y4 are individually one or more radicals selected from the group consisting of a hydrogen atom, lower alkyl radical, lower alkoxy radical, chlorine atom and bromine atom; and R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4˜9 carbon atoms, monocyclic aliphatic radical having 4˜10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member,
(2) a polyimide based resin composition comprising 1˜50 parts by weight of polyetherimide for 100 parts by weight of a resin composition comprised of 50˜1 parts by weight of polyarylether ketone and 50˜99 parts by weight of a polyimide having recurring structural units represented by the formula (3): ##STR6##
wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4˜9 carbon atoms, monocyclic aliphatic radical having 4˜10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member,
(3) a polyimide based resin composition wherein the polyimide comprises an end-capped polyimide polymer obtained by reacting diamine compound and tetracarboxylic dianhydride in the presence of aromatic dicarboxylic anhydride of the formula (4): ##STR7## wherein Z is a divalent radical having 6˜15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, and/or aromatic monoamine represented by the formula (5):
V--NH.sub.2                                                ( 5)
wherein V is a monovalent radical having 6˜15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member,
(4) a polyimide based resin composition wherein the polyarylether ketone comprises at least one selected from the group consisting of structural units represented by the formulae of from (6) to (10): ##STR8## (5) a polyimide based resin composition wherein the polyetherimide has recurring structural units represented by the formula (11): ##STR9## (6) a polyimide based resin composition improved a durability by heating at temperature of from 150° C. to 370° C.,
(7) a polyimide based resin composition which comprises 5 to 65 parts by weight of fibrous reinforcements for 100 parts by weight of the above polyimide based resin compositions, and
(8) an injection molded article obtained from the above polyimide based resin compositions.
The polyimide based resin composition of the present invention has excellent fatigue resistance, creep properties, and mechanical strength at a high temperature, and can be widely applied in the fields for parts which these characteristics is desired, for example, machine parts such as gears, shaft bushes, cams, bushings pulleys and sleeves; automobile parts such as impellers, manifolds, valve lifters, piston skirts, oil pans; and front covers, and chains.
DETAILED DESCRIPTION OF THE INVENTION
Polyimide used in the polyimide based resin composition of the present invention comprises one or more recurring structural units represented by the formula (1): ##STR10## wherein Ar and R are the same as above.
Exemplified polyimides include polyimide having recurring structural units represented by the formula (3): ##STR11## wherein R is the same as above, which Ar in the formula (1) is ##STR12## or polyimide having recurring structural units represented by the formula (2): ##STR13## wherein X, Y1 ˜Y4 and R are the same as above, which Ar in the formula (1) is ##STR14## wherein X and Y1 ˜Y4 are the same as above.
The polyimide used in the present invention can be prepared by the following processes.
Aromatic diamine compounds used as raw materials for the polyimide having recurring structural units represented by the formula (1) as fundamental skeleton are aromatic diamino compounds represented by the formula (1-1) ##STR15## that is, the aromatic diamine compounds are 1,3-bis(3-aminophenoxy)benzene represented by the formula (3-1): ##STR16## as a raw material for the polyimide having recurring structural units represented by the formula (3), and aromatic diamine compounds represented by the formula ( 2-1 ): ##STR17## wherein X is one or more radicals selected from the group consisting of a direct bond, divalent hydrocarbon radical having 1˜10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio, sulfonyl and ether radical, and Y1, Y2, Y3 and Y4 are individually one or more radicals selected from the group consisting of a hydrogen atom, lower alkyl radical, lower alkoxy radical, chlorine atom and bromine atom, as raw material for the polyimide having the recurring structural units represented by the formula (2).
The polyimide used in the present invention can be prepared by reacting one or more aromatic diamines with one or more tetracarboxylic dianhydrides represented by the formula (12): ##STR18## wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4˜9 carbon atoms, monocyclic aliphatic radical having 4˜10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, in a solvent and then thermally or chemically imidizing the resultant polyamic acid.
Exemplary diamine compounds represented by the above formula (2-1) include;
the diamine compound which X in the formula (2-1) is direct bond, for example;
4,4'-bis(3-aminophenoxy)biphenyl,
4,4'-bis(3-aminophenoxy)-3-methylbiphenyl,
4,4'-bis(3-aminophenoxy)-3,3'-dimethylbiphenyl,
4,4'-bis(3-aminophenoxy)-3,5-dimethylbiphenyl,
4,4'-bis(3-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl,
4,4'-bis(3-aminophenoxy)-3,3'-dichlorobiphenyl,
4,4'-bis(3-aminophenoxy)-3,5-dichlorobiphenyl,
4,4'-bis(3-aminophenoxy)-3,3',5,5'-tetrachlorobiphenyl,
4,4'-bis(3-aminophenoxy)-3,3'-dibromobiphenyl,
4,4'-bis(3-aminophenoxy)-3,5-dibromobiphenyl,
4,4'-bis(3-aminophenoxy)-3,3',5,5'-tetrabromobiphenyl,
2 the diamine compound which X in the formula (2-1) is divalent hydrocarbon radical, for example;
bis[4-(3-aminophenoxy)phenyl]methane,
1,1-bis[4-(3-aminophenoxy)phenyl]ethane,
1,2-bis[4-(3-aminophenoxy)phenyl]ethane,
2,2-bis[4-(3-aminophenoxy)phenyl]propane,
2-[4-(3-aminophenoxy)phenyl]-2-(4-(3-aminophenoxy)-3-methylphenyl]propane,
2,2-bis[4-(3-aminophenoxy)-3-methylphenyl]propane,
2-[4-(3-aminophenoxy)phenyl]-2-[4-(3-aminophenoxy)-3,5-dimethylphenyl]propane,
2,2-bis[4-(3-aminophenoxy)-3,5-dimethylphenyl]propane,
2,2-bis[4-(3-aminophenoxy)phenyl]butane,
3 the diamine compound which X in the formula (2-1) is hexafluorinated isopropylidene radical, for example;
2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,
4 the diamine compound which X in the formula (2-1) is carbonyl radical, for example;
bis[4-(3-aminophenoxy)phenyl]ketone,
bis[4-{4-4-aminophenoxy)phenoxy}phenyl]ketone,
5 the diamine compound which X in the formula (2-1) is thio radical, for example;
bis[4-(3-aminophenoxy)phenyl]sulfide,
bis[4-(3-aminophenoxy)-3-methoxyphenyl]sulfide,
[4-(3-aminophenoxy)phenyl]4-(3-aminophenoxy)-3,5-dimethoxyphenyl]sulfide,
bis[4-(3-aminophenoxy)-3,5-dimethoxyphenyl]sulfide,
6 the diamine compound which X in the formula (2-1) is sulfonyl radical, for example;
bis[4-(3-aminophenoxy)phenyl]sulfone,
bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone,
7 the diamine compound which X in the formula (2-1) is ether radical, for example;
bis[4-(3-aminophenoxy)phenyl]ether,
bis[4-(4-aminophenoxy)phenyl]ether.
These diamine compounds may be used either singly or in combination of two or more.
The polyimide used in the present invention is prepared by using the above aromatic diamine compound as raw materials. The polyimide prepared by simultaneous use of other diamines can also be used for the composition of the invention as long as no adverse effect is found on the good melt-flowability of the polyimide.
Other diamines which may be used as a mixture include, for example, m-aminobenzylamine, p-aminobenzylamine, bis(3-aminophenyl)ether, (3-aminophenyl)(4-aminophenyl)ether, bis(4-aminophenyl)ether, bis(3-aminophenyl)sulfide, (3-aminophenyl)(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis(3-aminophenyl)sulfone, (3-aminophenyl)(4-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfoxide, and bis[4-(4-aminophenoxy)phenyl]sulfone.
These aromatic diamine compounds are usually used with amount of less than 30% by weight per the essential aromatic diamine compound, preferably less than 5% by weight.
Tetracarboxylic dianhydride which is another raw material for preparing the polyimide used in the present invention is represented by the above formula (12).
In the tetracarboxylic dianhydride represented by the formula (12), R is one or more tetravalent radicals selected from the group consisting of from (a) to (e):
(a) an aliphatic radical having 4˜9 carbon atoms,
(b) an alicyclic radical having 4˜10 carbon atoms,
(c) a monoaromatic radical represented by the formula: ##STR19## (d) a condensed polyaromatic radical represented by the formula: ##STR20## (e) a noncondensed aromatic radical connected to each other with a direct bond or a bridge member and represented by the formula: ##STR21## wherein X1 is a direct bond, --O--, --S--, --SO2 --, --CH2 --, --CO-- ##STR22## wherein Y5 is direct bond, --O--, --S--, --SO2 --, --CH2 --, --CO--, ##STR23##
Tetracarboxylic dianhydrides for preparing the polyimide used in the present invention include, for example,
1 the tetracarboxylic dianhydride which R in the formula (12) is an aliphatic radical;
ethylenetetracarboxylic dianhydride,
butanetetracarboxylic dianhydride,
2 the tetracarboxylic dianhydride which R in the formula (12) is an alicyclic radical;
cyclopentanetetracarboxylic dianhydride,
3 the mono aromatic radical which R in the formula (12) is an alicyclic radical;
pyromellitic dianhydride,
1,2,3,4-benzenetetracarboxylic dianhydride,
4 the condensed polyaromatic radical which R in the formula (12) is an alicyclic radical;
2,3,6,7-naphthalenetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride,
3,4,9,10-perylenetetracarboxylic dianhydride,
2,3,6,7-anthracenetetracarboxylic dianhydride, and
1,2,7,8-phenanthrenetetracarboxylic dianhydride.
5 the tetracarboxylic dianhydride which R of the formula (12) is the following formula; ##STR24## and (1) wherein X1 in the above formula is direct bond; for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride,
2,2',3,3'-biphenyltetracarboxylic dianhydride;
(2) wherein X1 in the above formula is ether radical, for example, bis(3,4-dicarboxyphenyl)ether dianhydride;
(3) wherein X1 in the above formula is thio radical, for example, bis(3,4-dicarboxyphenyl)thioether dianhydride;
(4) wherein X1 in the above formula is an aliphatic radical such as --CH2 --, --C(CH3)2 -- and --C(CF3)2 --, for example,
bis(2,3-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)methane dianhydride,
1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,
2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride;
(5) wherein X1 of the above formula is a sulfonyl radical, for example,
bis(3,4-dicarboxyphenyl)sulfone dianhydride;
(6) wherein X1 of the above formula is a carbonyl radical, for example,
3,3',4,4'-benzophenonetetracarboxylic dianhydride,
2,2',3,3'-benzophenonetetracarboxylic dianhydride;
(7) wherein X1 of the above formula is another radical, for example,
1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride,
1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride,
1,3-bis(3,4-dicarboxybenzoyl)benzene dianhydride,
1,4-bis(3,4-dicarboxybenzoyl)benzene dianhydride,
2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl)propane dianhydride,
2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl)propane dianhydride,
bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl)ketone dianhydride,
bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl)ketone dianhydride,
4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride,
4,4'-bis[3-(1,2-dicarboxy)phenoxy]biphenyl dianhydride,
bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride,
bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride,
bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride,
bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride,
2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,2,2,2-hexafluoropropane dianhydride, and
2,2-bis {4-[3-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,2,2,2-hexafluoropropane dianhydride.
These tetracarboxylic dianhydrides may be used either singly or in combination of two or more.
The capped polyimide having at the polymer chain end an aromatic ring which is unsubstituted or substituted with a radical having no reactivity with amine or dicarboxylic anhydride, or the polyimide containing the end-capped polyimide, also may be used in the polyimide based resin composition of the present invention.
The end-capped polyimide can be prepared by reacting the above diamine compound with the above tetracarboxylic dianhydride in the presence of aromatic dicarboxylic anhydride of the formula (4): ##STR25## wherein Z is a divalent radical having 6˜15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, and/or aromatic monoamine represented by the formula (5):
V--NH.sub.2                                                ( 5)
wherein V is a monovalent radical having 6˜15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
Exemplary aromatic dicarboxylic anhydrides of the formula (4) include phthalic anhydride, 2,3-benzophenonedicarboxylic anhydride, 3,4-benzophenonedicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride and 1,9-anthracenedicarboxylic anhydride. These aromatic dicarboxylic anhydrides can be substituted with a radical having no reactivity with amine and dicarboxylic anhydride and may be used singly or as a mixture.
Phthalic anhydride is most preferred in view of properties and utility of polyimide obtained.
The amount of aromatic dicarboxylic anhydride used is 0.001˜1.0 mol per mol of the above aromatic diamine represented by the formula (2-1) or (3-1). An amount less than 0.001 mol leads to viscosity increase in processing at high temperatures and causes deterioration of processability. On the other hand, an amount exceeding 1.0 mol results in lowered mechanical properties. Preferred amount is in the range of 0.01 to 0.5 mol.
Aromatic monoamines of the formula (5) include, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-aminophenyl phenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene. These aromatic monoamines can be substituted with a radical having no reactivity with amine or dicarboxylic anhydride, and can be used singly or as a mixture. Aniline is most preferably used in view of properties and utility of polyimide obtained.
The amount of aromatic monoamine is 0.001˜1.0 mol per mol of the aromatic tetracarboxylic dianhydride represented by the above formula (12).
An amount less than 0.001 mol leads to a viscosity increase in processing at high temperatures and causes deterioration of processability. On the other hand, an amount exceeding 1.0 mol results in lowered mechanical properties. Preferred amount is in the range of 0.01˜0.5 mol.
Polyimide used in the present invention can be prepared by any known process. For example, preparation is carried out by the following processes.
(1) A process for preparing polyamic acid in an organic solvent isolating the polyamic acid by removing the solvent at a low temperature under reduced pressure or by pouring the resulting polyamic acid solution into a lean solvent, and imidizing the polyamic acid by heating to obtain polyimide.
(2) A process for preparing a polyamic acid solution by the same procedures as (1), chemically imidizing polyamic acid by addition of a dehydrating agent such as acetic anhydride optionally in the presence of a catalyst, successively isolating resultant polyimide by known procedures and, if desired, washing and drying the polyimide.
(3) A process for preparing polyamic acid solvent by the same procedures as (1) and successively conducting solution removal and thermal imidization at the same time by heating under reduced pressure.
(4) A process for mixing raw materials and solvents, and simultaneously conducting preparation of aromatic polyamic acid and imidization reaction thereof by heating optionally in the presence of a catalyst, azeotropic agent or dehydrating agent.
In the preparation of polyimide by these processes, it is particularly preferred to carry out the reaction in organic solvents.
Organic solvents which can be used include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, xylenols and anisole. These solvents can be used singly or as a mixture.
When polyimide is prepared in a solvent by using aromatic diamines, tetracarboxylic dianhydrides and dicarboxylic anhydrides or aromatic monoamines, these raw materials are charged and reacted by the following methods.
(1) A method for reacting tetracarboxylic dianhydride with aromatic diamine and successively adding dicarboxylic anhydride or aromatic monoamine to continue the reaction.
(2) A method for reacting aromatic diamine with dicarboxylic anhydride and successively adding tetracarboxylic dianhydride to continue the reaction. Alternatively, a method for reacting tetracarboxylic dianhydride with aromatic monoamine and successively adding aromatic diamine to continue the reaction.
(3) A method for simultaneously charging tetracarboxylic dianhydride aromatic diamine and dicarboxylic anhydride or aromatic monoamine to carry out the reaction.
Any of the above methods can be employed for progressing the reaction.
In these methods, the reaction temperature for polymerization and imidization is 300° C. or less. No particular limitation is imposed upon the reaction pressure, and the reaction can be sufficiently carried out under atmospheric pressure.
The reaction time differs depending upon diamine, tetracarboxylic dianhydride, solvent, catalyst and reaction temperature. The reaction time of 4˜24 hours is usually sufficient.
Polyimide having recurring structural units represented by the formula (1) used in the present invention usually has an inherent viscosity of 0.35˜1.0 dl/g, preferably 0.40˜0.95 dl/g, more preferably 0.4˜0.9 dl/g. When the inherent viscosity is less than 0.35 dl/g, mechanical strengths and durability of polyimide itself are insufficient. On the other hand, an inherent viscosity exceeding 1.0 dl/g, injection molding is very difficult because of poor processability. Inherent viscosity was measured at 35° C. after heat-dissolving polyimide in a solvent mixture composed of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol at a concentration of 0.5 g/100 ml.
Polyarylether ketone used in the polyimide based resin composition of the present invention includes a polyarylether ketone which comprises at least one selected from the group consisting of structural units represented by the formulae of from (6) to (10): ##STR26##
That is, the polyarylether ketone may be a homopolymer having one of structural unit selected from formulae (6)˜(10), or may be a copolymer having two or more of structural units selected from formulae (6)˜(10), or may be mixture comprising these homopolymers and/or copolymers.
The composition for polyarylether ketone and polyimide in the polyimide based resin composition comprises 50 to 1 parts by weight of polyarylether ketone and 50 to 99 parts by weight of polyimide having recurring structural units represented by the formula (1).
In the case of the composition comprising the polyimide having recurri-structural units of the formula (2), especially, the composition comprises 50 to 5 parts by weight of polyarylether ketone and 50 to 95 parts by weight of the polyimide.
When the amount of the polyarylether ketone exceeds 50 parts by weight, it is undesirable because of it's poor heat resistance, on the other hand, when the amount is less than 5 parts by weight, the effect for improving permanence properties is insufficient.
In the case of the composition comprising the polyimide having recurring structural units represented by the formula (3), the composition preferably comprises 50 to 1 parts by weight of polyarylether ketone and 50 to 99 parts by weight of the polyimide.
In this composition, an amount exceeding 50 parts by weight of the polyarylether ketone also tends to lower heat resistance of the polyimide, and an amount less than 1 parts by weight is insufficient to improve permanence properties.
Polyetherimide used in the polyimide based resin composition of the present invention has a recurring structural units represented by the following formula: ##STR27## wherein D is a trifunctional aromatic group where two functional groups out of three are connected with adjacent carbon atoms, both E and Ar1 are residue of divalent aromatic group.
The polyetherimide is a polymer consisting of ether and imide linkages as a required bonding unit and is substantially composed of recurring units which are represented by the above formula. Exemplary structural units of the polyetherimide are as follows; ##STR28## and E in these formula is residue of divalent aromatic group such as, ##STR29##
Especially, the polyetherimide represented by the formula (11) ##STR30## is preferably used in the present invention.
The polyetherimide is commercially available from General Electric Co. with the Trade Mark of ULTEM-1000.
An amount of polyetherimide in the polyimide based resin composition is 1 to 50 parts by weight for 100 parts by weight of a resin composition comprising 50 to 99 parts by weight of polyimide used in the present invention, that is, the polyimide represented by the formula (1), (2) or (3), and 50 to 1 parts by weight of polyarylether ketone, preferably 5 to 25 parts by weight, more preferably 10 to 20 parts by weight.
When an amount of polyetherimide exceeds 50 parts by weight, permanence properties of the composition decreases. On the other hand, an amount less than 1 part by weight does not lead to an outstandingly improving effect for permanence properties of the composition.
A satisfactory effect for improving permanence properties could not been obtained even though polyarylether ketone was added to polyimide having recurring structural units of the formula (1) and alloying the mixture. However, surprisingly, further addition of polyetherimide to the above resin mixture can remarkably improve the permanence properties of the resin mixture.
It is thought on the effect that polyimide and polyarylether ketone alone cannot provide sufficient compatibility whereas added polyetherimide acts as a compatibility enhancing agent between polyimide and polyarylether ketone, makes these components mutually soluble and improves durability of the polyimide based resin composition.
The polyimide based resin composition has also achieved a marked improvement on high temperature durability in addition to the improvement of permanence properties at room temperature. Thus good durability can also be maintained at high temperature.
No particular restriction is imposed upon the preparation process of the polyimide based resin composition. Any process can be applied as long as the process can provide the composition by mixing the above requisite components.
Usually, the following processes are often used.
1 A process for melt-extruding and pelletizing after mixing and pulverizing polyimide, polyarylether ketone and polyetherimide with a mortar, Henschel mixer, drum blender, tumbling blender, ball mill and ribbon blender.
2 A process for dissolving or uniformly dispersing polyimide, polyarylether ketone and polyetherimide in an organic solvent and successively removing the solvent to obtain a powder or film.
3 A process for adding polyarylether ketone and polyetherimide to an organic solvent solution of polyamic acid precursor of the polyimide, uniformly dissolving or dispersing the mixture, thermally imidizing polyamic acid by heating to 100°˜400° C. or chemically imidizing polyamic acid by using a common imidizing agent, and removing the solvent to obtain a powder or film.
In addition, the present resin composition can exhibit outstandingly improved mechanical strength, especially permanence properties, by heat treating the composition at the specified temperature.
The temperature for the heat-treatment is the range of from 150° to 370° C., preferably from 160° to 330° C., more preferably from 160° to 320° C.
Times for heat treatment varies depending upon treating temperature, usually, the time is at least 4 hours in the above temperature range.
Further, the polyimide based resin composition of the present invention includes another polyimide based resin composition reinforced by a fibrous reinforcement, which is comprised of the polyimide, the polyarylether ketone, the polyetherimide and a fibrous reinforcement.
Exemplary fibrous reinforcements which can be used in this composition include glass fibers, ceramic fibers, potassium titanate fibers, aromatic polyamide fibers, metal fibers, boron fibers, silicon carbide fibers, asbestos fibers, rock fibers and carbon fibers, preferably, glass fibers, aromatic polyamide fibers, potassium titanate fibers and carbon fibers.
The amount of the fibrous reinforcements used in the polyimide based resin composition is 5˜65 parts by weight for 100 parts by weight of the above resin composition comprised of the polyimide, the polyarylether ketone and the polyetherimide, preferably 10˜60 parts by weight. Thus, the polyimide based resin composition having excellent fatigue characteristics can be obtained by adding the fibrous reinforcements in the amount of the above range to the above resin composition.
In the polyimide based resin composition, further, one or more additives can be added, if desired.
Exemplary additives which can be used include, fillers such as calcium carbonate, mica, glass beads, graphite, molybdenum disulfide, clay, silica, alumina, talc, diatomaceous earth, hydration alumina and shirasu balloons; lubricants; release agents; stabilizers; colorants; crystalline nucleating agents; plasticizer; other noncrystalline resins such as polyether sulfone, polyether imide, polysulfone and polycarbonate; other crystalline resins such as polyphenylene sulfide, polyether nitrile, polyamide and polyamideimide, and thermosetting resins such as epoxy resin, silicone resin and polyamide imide resin.
The polyimide based resin composition of the present invention can provide various forms of articles, which have good resistance to fatigue and creep, by changing the mold for injection molding.
The articles by injection molding can be applied of the field in parts such as machine parts and automobile parts, wherein the noted characteristics are required.
The present invention will hereinafter be illustrated in detail by way of examples and comparative examples.
The properties of the composition obtained in each example and comparative example were tested by the following methods.
1) Fatigue test:
Tensile fatigue tests were carried out as follows by using ASTM No.1 Dumbbell specimens obtained in the examples and comparative examples.
(1) The number of repetitions until the specimen was broken was measured under the conditions; 5 Hz, stress amplitude 5.5 kg/mm2, stress ratio=0, at room temperature.
(2) The number repetitions until the specimen was broken was measured under the conditions; 30 Hz, stress amplitude 12kg/mm2, stress ratio=0, at room temperature.
2) High temperature fatigue test:
Tensile fatigue tests at a high temperature were carried out as follows by using ASTM No.1 Dumbbell specimens obtained in the examples and comparative examples.
(1) The number of repetitions until the specimen was broken was measured under the conditions: 5 Hz, stress amplitude 3.0 kg/mm2, stress ratio=0, at 140° C.
(2) The number of repetitions until the specimen was broken was measured under the conditions; 30 Hz, stress amplitude 8 kg/mm2, stress ratio=0, at 140° C.
(3) The number of repetitions until the specimen was broken was measured under the conditions; 30Hz, stress amplitude 10 kg/mm2, stress ratio=0, at 140° C.
3) Tensile Strength:
Measured in accordance with ASTM D-638.
4) Creep strength at break(kg/mm2):
In the creep test, the stress which caused the first break at 1500 hours was measured.
5) Creep strength at break(%):
The ratio of tensile strength in the above 3) to the above creep strength at break was calculated.
6) Heat distortion temperature (HDT):
Measured in accordance with ASTM D-648.
7) Tensile strength at 150° C. (kg/mm2):
Measured in accordance with ASTM D-638.
The polyarylether ketones used in the examples and comparative examples have individually the following structural units.
1) PEEK (PEEK 450 P; Trade Mark of Imperial Chemicals Industries Ltd.) ##STR31## 2) PEKEKK (ULTRA PEK A-1000; Trade Mark of B.A.S.F.) ##STR32## 3) PEK (PEK 220; Trade Mark of Imperial Chemicals Industries Ltd.) ##STR33##
Example 1
For 90 parts by weight of polyimide which was prepared from 4,4'-bis(3-aminophenoxy)biphenyl and pyromellitic dianhydride and had an inherent viscosity of 0.50 dl/g and 10 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of General Electric Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370°˜400° C. and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 900 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 1.
Examples 2˜10
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in examples 2˜10 in Table 1 were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 1.
Examples 11 and 12
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in examples 11 and 12 in Table 1 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 1.
Example 13
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in example 13 in Table 1 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 1.
                                  TABLE 1                                 
__________________________________________________________________________
         Example 1                                                        
                Example 2                                                 
                      Example 3                                           
                            Example 4                                     
                                  Example 5                               
                                        Example 6                         
                                              Example 7                   
__________________________________________________________________________
Composition                                                               
(parts by weight)                                                         
Polyimide                                                                 
         90     80    70    60    60    60    60                          
Polyarylether-                                                            
         10     20    30    40    40    40    40                          
ketone                                                                    
Polyetherimide                                                            
         5      15    15    2     5     15    25                          
Carbon fiber                                                              
         --     --    --    --    --    --    --                          
Fatigue test*.sup.1                                                       
         1.1 × 10.sup.5                                             
                1.1 × 10.sup.5                                      
                      1.3 × 10.sup.5                                
                            0.7 × 10.sup.5                          
                                  1.2 × 10.sup.5                    
                                        1.5 × 10.sup.5              
                                              1.3 × 10.sup.5        
(5.5 kg/mm.sup.2)*.sup.2                                                  
High temperature                                                          
         7.5 × 10.sup.4                                             
                8.0 × 10.sup.4                                      
                      8.8 × 10.sup.4                                
                            0.6 × 10.sup.4                          
                                  1.5 × 10.sup.4                    
                                        9.0 × 10.sup.4              
                                              8.5 × 10.sup.4        
fatigue test*.sup.1                                                       
(3.0 kg/mm.sup.2)*.sup.2                                                  
Tensile strength                                                          
         11.5   11.6  11.1  11.4  11.4  11.5  11.3                        
(kg/mm.sup.2)                                                             
Creep strength at                                                         
         8.5    8.9   9.1   8.6   8.9   9.2   9.9                         
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
         74     77    82    75    78    80    88                          
break (%)                                                                 
HDT (°C.)*.sup.3                                                   
         220    216   213   216   214   210   210                         
Kind of polyaryl-                                                         
         PEEK 450 P                                                       
                ←                                                    
                      ←                                              
                            ←                                        
                                  ←                                  
                                        ←                            
                                              ←                      
ether ketone                                                              
__________________________________________________________________________
               Example 8                                                  
                     Example 9                                            
                            Example 10                                    
                                  Example 11                              
                                        Example 12                        
                                              Example 13                  
__________________________________________________________________________
Composition                                                               
(parts by weight)                                                         
Polyimide      60    80     60    80    60    70                          
Polyarylether- 40    20     40    20    40    30                          
ketone                                                                    
Polyetherimide 43    25     25    15    15    10                          
Carbon fiber   --    --     --    --    --    --                          
Fatigue test*.sup.1                                                       
               0.7 × 10.sup.5                                       
                     1.0 × 10.sup.5                                 
                            1.3 × 10.sup.5                          
                                   5.0 × 10.sup.5                   
                                         6.2 × 10.sup.5             
                                               8.0 × 10.sup.5       
(5.5 kg/mm.sup.2)*.sup.2                                                  
High temperature                                                          
               7.2 × 10.sup.4                                       
                     7.6 × 10.sup.4                                 
                            8.3 × 10.sup.4                          
                                  11.0 × 10.sup.4                   
                                        23.5 ×  10.sup.4            
                                              40.3 × 10.sup.4       
fatigue test*.sup.1                                                       
(3.0 kg/mm.sup.2)*.sup.2                                                  
Tensile strength                                                          
               10.6  11.8   10.7  9.8   9.8   10.2                        
(kg/mm.sup.2)                                                             
Creep strength at                                                         
               8.5   8.9    9.2   9.0   9.0   9.0                         
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
               80    75     86    92    92    88                          
break (%)                                                                 
HDT (°C.)*.sup.3                                                   
               208   212    208   226   220   219                         
Kind of polyaryl-                                                         
               ←                                                     
                     PEEK 450 P                                           
                            ←                                        
                                  PEKEKK                                  
                                        ←                            
                                              PEK220                      
ether ketone                      A-1000                                  
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetition until the specimen was broken.              
 *.sup.2 Stress                                                           
 *3.sup. HDT--Heat distortion temperature
Comparative Example 1
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 1 in Table 2 were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
Comparative Example 2
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 2 in Table 2 and PEEK (PEEK 450 P; Trade Mark of I.C.I.Ltd.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
Comparative Example 3
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 3 in Table 2 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
Comparative Example 4
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 4 in Table 2 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
Comparative Example 5
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 5 in Table 2 and PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
Comparative Example 6
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 6 in Table 2 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
Comparative Example 7
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that compositions illustrated in comparative example 7 in Table 2 and PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
Comparative Example 8
Test specimens were prepared by carrying out the same procedures as described in Example 1 except that PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 2.
                                  TABLE 2                                 
__________________________________________________________________________
          Compara.                                                        
                Compara.                                                  
                       Compara.                                           
                             Compara.                                     
                                   Compara.                               
                                          Compara.                        
                                                 Compara.                 
                                                        Compara.          
          example 1                                                       
                example 2                                                 
                       example 3                                          
                             example 4                                    
                                   example 5                              
                                          example 6                       
                                                 example                  
                                                        example           
__________________________________________________________________________
                                                        8                 
Composition                                                               
(parts by weight)                                                         
Polyimide 100   60     60    70    60     60     30     --                
Polyarylether-                                                            
          --    40     40    30    40     40     70     100               
ketone                                                                    
Polyetherimide                     70     80     15                       
Carbon fiber                                                              
          --    --     --    --    --     --     --     --                
Fatigue test*.sup.1                                                       
          0.2 × 10.sup.5                                            
                0.5 × 10.sup.5                                      
                       0.8 × 10.sup.5                               
                             0.9 × 10.sup.5                         
                                   0.2 × 10.sup.5                   
                                          0.4 × 10.sup.5            
                                                 9.0 × 10.sup.5     
                                                        1.0 ×       
                                                        10.sup.7          
(5.5 kg/mm.sup.2)*.sup.2                                unbroken          
High temperature                                                          
          1.0 × 10.sup.4                                            
                0.5 × 10.sup.4                                      
                       4.7 × 10.sup.4                               
                             3.2 × 10.sup.4                         
                                   0.5 × 10.sup.4                   
                                          2.3 × 10.sup.4            
                                                 0.2 × 10.sup.4     
                                                        0.1 ×       
                                                        10.sup.4          
fatigue test*.sup.1                                                       
(3.0 kg/mm.sup.2)*.sup.2                                                  
Tensile strength                                                          
          8.8   10.2   9.9   10.0  10.2   10.3   10.0   10.6              
(kg/mm.sup.2)                                                             
Creep strength at                                                         
          5.9   7.3    7.4   7.5   7.8    8.0    8.8    9.4               
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
          67    72     75    75    76     78     88     89                
break (%)                                                                 
HDT (°C.)*.sup.3                                                   
          220   216    213   210   212    208    170    158               
Kind of polyaryl-                                                         
          --    PEEK 450 P                                                
                       PEKEKK                                             
                             PEK 220                                      
                                   PEEK 450 P                             
                                          PEKEKK PEEK 450                 
                                                        ←            
ether ketone           A-1000             A-1000                          
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetition until the specimen was broken.              
 *.sup.2 Stress                                                           
 *.sup.3 HDT--Heat distortion temperature
Example 14
For 60 parts by weight of polyimide which was prepared from 4,4'-bis(3-aminophenoxy)biphenyl and pyromellitic dianhydride and had an inherent viscosity of 0.50 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370°˜420° C. While charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 3.
Examples 15˜18
Test specimens were prepared by carrying out the same procedures as described in Example 14 except that resin composition and carbon fiber illustrated in examples 15˜18 in Table 3, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 3.
Comparative Examples 9 and 10
Test specimens were prepared by carrying out the same procedures as described in Example 14 except that resin and carbon fiber illustrated in comparative examples 9 and 10 in Table 3, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 3.
                                  TABLE 3                                 
__________________________________________________________________________
                                         Compara.                         
                                               Compara.                   
          Example 14                                                      
                 Example 15                                               
                       Example 16                                         
                             Example 17                                   
                                   Example 18                             
                                         example 9                        
                                               example 10                 
__________________________________________________________________________
Composition                                                               
(parts by weight)                                                         
Polyimide 60     60    60    80    60    100   --                         
Polyarylether-                                                            
          40     40    40    20    40    --    100                        
ketone                                                                    
Polyether imide                                                           
          5      15    25    15    15    --    --                         
Carbon fiber*.sup.4                                                       
          43     43    43    43    43    43    43                         
Fatigue test*.sup.1                                                       
          0.9 × 10.sup.6                                            
                 1.0 × 10.sup.6                                     
                       1.5 × 10.sup.6                               
                             1.0 × 10.sup.6                         
                                   3.0 × 10.sup.6                   
                                         1.0 × 10.sup.5             
                                                1.0 × 10.sup.7      
(12 kg/mm.sup.2)*.sup.2                        unbroken                   
High temperature                                                          
          3.0 × 10.sup.6                                            
                 4.5 × 10.sup.6                                     
                       4.1 × 10.sup.6                               
                             2.0 × 10.sup.6                         
                                   8.0 × 10.sup.6                   
                                         0.1 × 10.sup.6             
                                               0.05 × 10.sup.6      
fatigue test*.sup.1                                                       
(10 kg/mm.sup.2)*.sup.2                                                   
Tensile strength                                                          
          25.5   26.0  25.9  26.5  27.1  24.1  26.0                       
(kg/mm.sup.2)                                                             
Creep strength at                                                         
          19.4   20.8  20.5  20.0  21.5  16.6  23.1                       
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
          76     80    79    75    79    69    89                         
break (%)                                                                 
Tensile strength at                                                       
          13.9   14.1  14.1  14.1  13.6  15.0  11.5                       
150° C. (kg/mm.sup.2)                                              
Kind of polyaryl-                                                         
          PEEK 450 P                                                      
                 ←                                                   
                       ←                                             
                             ←                                       
                                   ←                                 
                                         --    PEEK 450 P                 
ether ketone                                                              
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress                                                           
 *.sup.3 HDT--Heat distortion temperature                                 
 *.sup.4 Parts by weight for 100 parts by weight of resin composition
Example 19
For 60 parts by weight of polyimide which was prepared from 4,4'-bis(3-aminophenoxy)biphenyl and pyromellitic dianhydride and had an inherent viscosity of 0.50 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 15 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370°˜420° C. while charging from a side feeder 5 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 4.
Examples 20˜23
Test specimens were prepared by carrying out the same procedures as described in Example 19 except that carbon fiber illustrated in examples 20˜23 in Table 4, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 4.
                                  TABLE 4                                 
__________________________________________________________________________
          Example 19                                                      
                 Example 20                                               
                       Example 21                                         
                             Example 22                                   
                                   Example 23                             
__________________________________________________________________________
Composition                                                               
(parts by weight)                                                         
Polyimide 60     60    60    60    60                                     
Polyarylether-                                                            
          40     40    40    40    40                                     
ketone                                                                    
Polyether imide                                                           
          15     15    15    15    15                                     
Carbon fiber*.sup.4                                                       
          5      43    65    --    85                                     
Fatigue test*.sup.1                                                       
          8.0 × 10.sup.3                                            
                 1.0 × 10.sup.6                                     
                       1.0 × 10.sup.7                               
                             broke in                                     
                                   Poor                                   
(12 kg/mm.sup.2)*.sup.2                                                   
                       unbroken                                           
                             early flowability                            
                             stage                                        
                             of test                                      
High temperature                                                          
          1.0 × 10.sup.4                                            
                 1.0 × 10.sup.7                                     
                       1.0 × 10.sup.7                               
                             broke in                                     
fatigue test*.sup.1                                                       
                 unbroken                                                 
                       unbroken                                           
                             early                                        
(8 kg/mm.sup.2)*.sup.2       stage                                        
                             of test                                      
Tensile strength                                                          
          15.0   26.0  29.0  11.5                                         
(kg/mm.sup.2)                                                             
Creep strength at                                                         
          12.0   20.8  23.2  9.2                                          
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
          80     80    80    80                                           
break (%)                                                                 
Tensile strength at                                                       
          8.3    14.1  15.3  6.2                                          
150° C. (kg/mm.sup.2)                                              
Kind of polyaryl-                                                         
          PEEK 450 P                                                      
                 ←                                                   
                       ←                                             
                             ←                                       
                                   ←                                 
ether ketone                                                              
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress                                                           
 *.sup.3 HDT--Heat distortion temperature                                 
 *.sup.4 Parts by weight for 100 parts by weight of resin composition
Example 24
For 80 parts by weight of polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 20 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370°˜400° C. and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 900 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 5.
Examples 25˜32
Test specimens were prepared by carrying out the same procedures as described in Example 24 except that compositions illustrated in comparative example 25˜32 in Table 5, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 5.
                                  TABLE 5                                 
__________________________________________________________________________
         Example 24                                                       
               Example 25                                                 
                     Example 26                                           
                           Example 27                                     
                                 Example 28                               
                                       Example 29                         
                                             Example 30                   
                                                   Example                
                                                         Example          
__________________________________________________________________________
                                                         32               
Composition                                                               
(parts by weight)                                                         
Polyimide                                                                 
         80    80    80    60    60    60    60    60    60               
Polyarylether-                                                            
         20    20    20    40    40    40    40    40    40               
ketone                                                                    
Polyetherimide                                                            
         5     10    25    2     5     10    20    25    43               
Carbon fiber                                                              
         --    --    --    --    --    --    --    --    --               
Fatigue test*.sup.1                                                       
         4.8 × 10.sup.5                                             
               5.0 × 10.sup.5                                       
                     4.6 × 10.sup.5                                 
                           5.0 × 10.sup.5                           
                                 7.0 × 10.sup.5                     
                                       7.9 × 10.sup.5               
                                             9.8 × 10.sup.5         
                                                   9.5 × 10.sup.5   
                                                         5.2 ×      
                                                         10.sup.5         
(5.5 kg/mm.sup.2)*.sup.2                                                  
High temperature                                                          
         1.0 × 10.sup.5                                             
               2.3 × 10.sup.5                                       
                     1.6 × 10.sup.5                                 
                           0.5 × 10.sup.5                           
                                 0.9 × 10.sup.5                     
                                       2.6 × 10.sup.5               
                                             3.6 × 10.sup.5         
                                                   4.2 × 10.sup.5   
                                                         1.1 ×      
                                                         10.sup.5         
fatigue test*.sup.1                                                       
(3.0 kg/mm.sup.2)*.sup.2                                                  
Tensile strength                                                          
         11.8  11.9  11.7  11.8  12.0  12.2  12.6  12.6  12.3             
(kg/mm.sup.2)                                                             
Creep strength at                                                         
         9.4   9.5   9.9   9.4   9.8   10.2  11.0  11.2  10.5             
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
         80    80    85    80    82    84    87    89    85               
break (%)                                                                 
HDT (°C.)                                                          
         223   220   220   218   216   214   214   215   213              
Heat treatment                                                            
         non treated                                                      
               ←                                                     
                     ←                                               
                           ←                                         
                                 ←                                   
                                       ←                             
                                             ←                       
                                                   ←                 
                                                         ←           
Kind of polyaryl-                                                         
         PEEK  ←                                                     
                     ←                                               
                           ←                                         
                                 ←                                   
                                       ←                             
                                             ←                       
                                                   ←                 
                                                         ←           
ether ketone                                                              
         450 P                                                            
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress                                                           
 *.sup.3 HDT--Heat distortion temperature
Example 33
Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in example 33 in Table 6 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 6.
Example 34
Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in example 33 in Table 6 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 6.
Example 35
Test specimens obtained in Example 34 were heat-treated for 4 hours at 220° C.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 6.
Example 36
For 60 parts by weight of polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of aniline as end-capping agent and had an inherent viscosity of 0.65 dl/g and 40 parts by weight of polyarylether ketone (PEKEKK) (ULTAR PEK A-1000; Trade Mark of B.A.S.F.), 10 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twice screw extruder at 370°˜400° C. and cut in to pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 900 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 6.
Example 37
Test specimens obtained in Example 36 were heat-treated for 4 hours at 220° C.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 6.
                                  TABLE 6                                 
__________________________________________________________________________
         Example 33                                                       
               Example 34                                                 
                      Example 35                                          
                            Example 36                                    
                                  Example 37                              
__________________________________________________________________________
Composition                                                               
(parts by weight)                                                         
Polyimide                                                                 
         60    60     60    60    60                                      
Polyarylether-                                                            
         40    40     40    40    40                                      
ketone                                                                    
Polyetherimide                                                            
         10    10     10    10    10                                      
Carbon fiber                                                              
         --    --     --    --    --                                      
Fatigue test*.sup.1                                                       
         60.0 × 10.sup.5                                            
               49.8 × 10.sup.5                                      
                      88.9 × 10.sup.5                               
                            49.2 × 10.sup.5                         
                                  80.9 × 10.sup.5                   
(5.5 kg/mm.sup.2)*.sup.2                                                  
High temperature                                                          
          8.0 × 10.sup.5                                            
               10.0 × 10.sup.5                                      
                      60.3 × 10.sup.5                               
                             6.7 × 10.sup.5                         
                                  33.4 × 10.sup.5                   
fatigue test*.sup.1                                                       
(3.0 kg/mm.sup.2)*.sup.2                                                  
Tensile strength                                                          
         11.5  11.3   13.1  11.2  12.9                                    
(kg/mm.sup.2)                                                             
Creep strength at                                                         
         10.4  10.1   12.2  10.0  12.0                                    
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
         90    89     93    89    93                                      
break (%)                                                                 
HDT (°C.)*.sup.3                                                   
         220   219    220   219   220                                     
Heat treatment                                                            
         non treated                                                      
               ← treated                                             
                            non treated                                   
                                  treated                                 
Kind of polyaryl-                                                         
         PEKEKK                                                           
               PEK 220                                                    
                      ←                                              
                            PEKEKK                                        
                                  ←                                  
ether ketone                                                              
         A-1000             A-1000                                        
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress                                                           
 *.sup.3 HDT--Heat distortion temperature
Comparative Example 11
Polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end capping agent and had an inherent viscosity of 0.65 dl/g extruded through a twin screw extruder at 370°˜400° C. and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 900 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 7.
Comparative Examples 12˜15
Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in comparative examples 12˜15 in Table 7 and PEEK (PEEK 450 P; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, are used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 7.
Comparative Example 16
Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in comparative example 16 in Table 7 and PEKEKK (ULTRA PEK A-1000; Trade Mark of B.A.S.F.) as polyarylether ketone, are used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 7.
Comparative Example 17
Test specimens were prepared by carrying out the same procedures as described in Example 24 except that composition illustrated in comparative example 17 in Table 7 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, are used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 7.
Comparative Example 18
Polyarylketone (PEEK 450 P; Trade mark; I.C.I. Ltd.) extruded through a twice screw extruder at 370°˜400° C. and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 360°˜380° C., injection pressure of 900 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 7.
                                  TABLE 7                                 
__________________________________________________________________________
          Comparative                                                     
                 Compara.                                                 
                        Compara.                                          
                              Compara.                                    
                                    Compara.                              
                                          Compara.                        
                                                 Compara.                 
                                                       Compara.           
          example 11                                                      
                 example 12                                               
                        example 13                                        
                              example 14                                  
                                    example 15                            
                                          example 16                      
                                                 example                  
                                                       example            
__________________________________________________________________________
                                                       18                 
Composition                                                               
(parts by weight)                                                         
Polyimide 100    80     60    60    30    60     60    --                 
Polyarylether-                                                            
          --     20     40    40    70    40     40    100                
ketone                                                                    
Polyetherimide                                                            
          --     --     --    80    10    --     --    --                 
Carbon fiber                                                              
          --     --     --    --    --    --     --    --                 
Fatigue test*.sup.1                                                       
          0.7 × 10.sup.5                                            
                 1.0 × 10.sup.5                                     
                        2.0 × 10.sup.5                              
                              0.9 × 10.sup.5                        
                                    9.9 × 10.sup.5                  
                                           7.1 × 10.sup.5           
                                                  8.0 × 10.sup.5    
                                                       1.0 ×        
                                                       10.sup.7           
(5.5 kg/mm.sup.2)*.sup.2                               unbroken           
High temperature                                                          
          3.0 × 10.sup.4                                            
                 1.0 × 10.sup.4                                     
                        0.5 × 10.sup.4                              
                              8.0 × 10.sup. 4                       
                                    0.2 × 10.sup.4                  
                                          10.0 × 10.sup.4           
                                                 12.0 × 10.sup.4    
                                                       0.1 ×        
                                                       10.sup.4           
fatigue test*.sup.1                                                       
(3.0 kg/mm.sup.2)*.sup.2                                                  
Tensile strength                                                          
          9.2    10.1   10.7  10.7  10.2  10.9   10.8  10.6               
(kg/mm.sup.2)                                                             
Creep strength at                                                         
          6.3    7.4    8.1   7.6   9.1   9.5    9.2   9.4                
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
          69     73     76    71    89    87     85    89                 
break (%)                                                                 
HDT (°C.)*.sup.3                                                   
          220    222    215   209   178   218    217   158                
Heat treatment                                                            
          non treated                                                     
                 ← ←                                            
                              ←                                      
                                    ←                                
                                          ← ←                   
                                                       ←             
Kind of polyaryl-                                                         
          --     PEEK 450 P                                               
                        ←                                            
                              ←                                      
                                    ←                                
                                          PEKEKK PEK 220                  
                                                       PEEK 450 P         
ether ketone                              A-1000                          
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress                                                           
 *.sup.3 HDT--Heat distortion temperature
Example 38
For 60 parts by weight of polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I.Ltd.), 5 parts by weight of polyetherimide (ULTEM 1000; Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370°˜420° C. While charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 8.
Examples 39˜40
Composition of examples 39˜40 illustrated in Table 8 was dryblended respectively and successively extruded through a twin screw extruder at 370°˜420° C. while charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 8.
Example 41
For 80 parts by weight of polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 20 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 15 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370°˜420° C. while charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 160° C. to form test specimens.
The test specimens obtained above were heat-treated for 4 hours at 220° C.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 8.
Example 42
Test specimens were prepared by carrying out the same procedures as described in Example 41 except that composition illustrated in example 42 in Table 8 and PEK (PEK 220; Trade Mark of I.C.I. Ltd.) as polyarylether ketone, are used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 8.
Example 43
Test specimens were prepared by carrying out the same procedures as described in Example 41 except that composition illustrated in example 43 in Table 8 and PEKEKK (ULTRA PEK A 1000; Trade Mark of B.A.S.F.) as polyarylether ketone, are used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 8.
Example 44
Test specimens obtained in Example 38 were heat-treated for 4 hours at 220° C.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 8.
                                  TABLE 8                                 
__________________________________________________________________________
          Example 38                                                      
                 Example 39                                               
                       Example 40                                         
                             Example 41                                   
                                   Example 42                             
                                          Example 43                      
                                                Example                   
__________________________________________________________________________
                                                44                        
Composition                                                               
(parts by weight)                                                         
Polyimide 60     60    60    80    80     80    60                        
Polyarylether-                                                            
          40     40    40    20    20     20    40                        
ketone                                                                    
Polyetherimide                                                            
          5      15    25    15    15     15    15                        
Carbon fiber*.sup.4                                                       
          43     43    43    43    43     43    43                        
Fatigue test*.sup.1                                                       
          0.08 × 10.sup.7                                           
                 0.1 × 10.sup.7                                     
                       0.8 × 10.sup.7                               
                             0.6 × 10.sup.7                         
                                   1.0 × 10.sup.7                   
                                          1.0 × 10.sup.7            
                                                0.7 × 10.sup.7      
(12 kg/mm.sup.2)*.sup.2            unbroken                               
                                          ←                          
High temperature                                                          
           9.0 × 10.sup.6                                           
                 1.0 × 10.sup.7                                     
                       1.0 × 10.sup.7                               
                             1.0 × 10.sup.7                         
                                   1.0 × 10.sup.7                   
                                          1.0 × 10.sup.7            
                                                1.0 × 10.sup.7      
fatigue test*.sup.1                                                       
(10 kg/mm.sup.2)*.sup.2                                                   
                 unbroken                                                 
                       ←                                             
                             ←                                       
                                   ← ←                          
                                                ←                    
Tensile strength                                                          
          26.9   27.1  27.7  28.2  29.1   30.1  28.9                      
(kg/mm.sup.2)                                                             
Creep strength at                                                         
          22.9   23.8  24.7  24.0  25.9   26.5  26.0                      
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
          85     88    89    85    89     88    90                        
break (%)                                                                 
Tensile strength at                                                       
          13.3   13.8  14.3  14.5  15.1   15.2  14.1                      
150° C. (kg/mm.sup.2)                                              
Heat treatment                                                            
          non treated                                                     
                 ←                                                   
                       ←                                             
                             treated                                      
                                   ← ←                          
                                                ←                    
Kind of polyaryl-                                                         
          PEEK 450 P                                                      
                 ←                                                   
                       ←                                             
                             ←                                       
                                   PEK 220                                
                                          PEKEKK                          
                                                PEEK 450 P                
ether ketone                              A-1000                          
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress                                                           
 *.sup.3 HDT--Heat distortion temperature                                 
 *.sup.4 Parts by weight for 100 parts by weight of resin composition
Comparative Example 19
Polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g extruded through a twin screw extruder at 370°˜420° C. while charging from a side feeder 43 parts by weight of carbon fiber for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 9.
Comparative Example 20
Test specimens obtained in comparative example 19 were heat-treated for 4 hours at 220° C.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 9.
Comparative Example 21
Polyarylether ketone (PEEK 450 CF 30 weight % pellet; Trade mark: I.C.I. Ltd.) were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 180° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 9.
              TABLE 9                                                     
______________________________________                                    
          Comparative                                                     
                   Compara.  Compara.                                     
          example 19                                                      
                   example 20                                             
                             example 21                                   
______________________________________                                    
Composition                                                               
(parts by weight)                                                         
Polyimide   100        100       --                                       
Polyarylether-                                                            
            --         --        100                                      
ketone                                                                    
Polyetherimide                                                            
            --         --        --                                       
Carbon fiber*.sup.4                                                       
            43         43        43                                       
Fatigue test*.sup.1                                                       
            4.0 × 10.sup.4                                          
                       4.0 × 10.sup.4                               
                                  1.0 × 10.sup.7                    
(12 kg/mm.sup.2)*.sup.2          unbroken                                 
High temperature                                                          
            0.3 × 10.sup.6                                          
                       0.3 × 10.sup.6                               
                                 0.05 × 10.sup.6                    
fatigue test*.sup.1                                                       
(10 kg/mm.sup.2)*.sup.2                                                   
Tensile strength                                                          
            24.9       24.9      26.0                                     
(kg/mm.sup.2)                                                             
Creep strength at                                                         
            17.2       17.2      23.1                                     
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
            69         69        89                                       
break (%)                                                                 
Tensile strength at                                                       
            15.3       15.3      11.5                                     
150° C. (kg/mm.sup.2)                                              
Heat treatment                                                            
            non treated                                                   
                       treated   non treated                              
Kind of polyaryl-                                                         
            --         --        PEEK 450 P                               
ether ketone                                                              
______________________________________                                    
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress.                                                          
 *.sup.3 HDT-- Heat distortion temperature                                
 *.sup.4 Parts by weight for 100 parts by weight of resin composition
Example 45
For 60 parts by weight of polyimide which was prepared from 1,3-bis(3-aminophenoxy)benzene and pyromellitic dianhydride in the presence of phthalic anhydride as end-capping agent and had an inherent viscosity of 0.65 dl/g and 40 parts by weight of polyarylether ketone (PEEK 450 P; Trade Mark of I.C.I. Ltd.), 15 parts by weight of polyetherimide (ULTEM 1000: Trade Mark of G.E. Co.) was dry blended with a mixer, successively extruded through a twin screw extruder at 370°˜420° C. while charging from a side feeder 5 parts by weight of carbon fibers for 100 parts by weight of the resin composition and cut into pellets. The pellets thus obtained were injection molded at cylinder temperature of 370°˜410° C., injection pressure of 2300 kg/cm2 and mold temperature of 160° C. to form test specimens.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 10.
Examples 46˜49
Test specimens were prepared by carrying out the same procedures as described in Example 45 except that carbon fibers illustrated in examples 46˜49 in Table 10, were used.
Various properties were measured by these specimens. Test items, test methods and results are illustrated in Table 10.
                                  TABLE 10                                
__________________________________________________________________________
          Example 45                                                      
                 Example 46                                               
                       Example 47                                         
                             Example 48                                   
                                   Example 49                             
__________________________________________________________________________
Composition                                                               
(parts by weight)                                                         
Polyimide 60     60    60    60    60                                     
Polyarylether-                                                            
          40     40    40    40    40                                     
ketone                                                                    
Polyetherimide                                                            
          15     15    15    15    15                                     
Carbon fiber*.sup.4                                                       
          5      43    65    --    85                                     
Fatigue test*.sup.1                                                       
          5.0 × 10.sup.4                                            
                 1.0 × 10.sup.6                                     
                       1.0 × 10.sup.7                               
                             broke in                                     
                                   poor flow-                             
(12 kg/mm.sup.2)*.sup.2                                                   
                       unbroken                                           
                             early ability                                
                             stage                                        
                             of test                                      
High temperature                                                          
          7.0 × 10.sup.5                                            
                 1.0 × 10.sup.7                                     
                       1.0 × 10.sup.7                               
                             broke in                                     
fatigue test*.sup.1                                                       
                 unbroken                                                 
                       unbroken                                           
                             early                                        
(8 kg/mm.sup.2)*.sup.2       stage                                        
                             of test                                      
Tensile strength                                                          
          16.3   27.1  29.9  12.4                                         
(kg/mm.sup.2)                                                             
Creep strength at                                                         
          14.0   23.8  27.5  10.5                                         
break (kg/mm.sup.2)                                                       
Creep strength at                                                         
          86     88    92    85                                           
break (%)                                                                 
Tensile strength at                                                       
          9.2    13.8  15.9  7.5                                          
150° C. (kg/mm.sup.2)                                              
Heat treatment                                                            
          non treated                                                     
                 ←                                                   
                       ←                                             
                             ←                                       
Kind of polyaryl-                                                         
          PEEK 450 P                                                      
                 ←                                                   
                       ←                                             
                             ←                                       
                                   ←                                 
ether ketone                                                              
__________________________________________________________________________
 note)                                                                    
 *.sup.1 Number of repetitions until the specimen was broken.             
 *.sup.2 Stress.                                                          
 *.sup.3 HDT--Heat distortion temperature                                 
 *.sup.4 Parts by weight for 100 parts by weight of resin composition

Claims (11)

What is claimed is:
1. A polyimide based resin composition having good resistance to fatigue and creep, comprising 1˜50 parts by weight of polyetherimide for 100 parts by weight of a resin composition comprised of 50˜1 parts by weight of polyarylether ketone and 50˜99 parts by weight of a polyimide having recurring structural units represented by the formula (1): ##STR34## wherein Ar is ##STR35## wherein X is one or more radicals selected from the group consisting of a direct bond, divalent hydrocarbon radical having 1˜10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio, sulfonyl and ether radical, and Y1, Y2, Y3, and Y4 are individually one or more radicals selected from the group consisting of a halogen atom, lower alkyl radical,lower alkoxy radical, chlorine atom and bromine atom; and R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4˜9 carbon atoms, monocyclic aliphatic radical having 4˜10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member and wherein the polyimide is different from the polyetherimide.
2. A polyimide based resin composition comprising 1˜50 parts by weight of polyetherimide for 100 parts by weight of a resin comprising comprised of 50˜5 parts by weight of polyarylether ketone and 50˜95 parts by weight of a polyimide having recurring structural units represented by the formula (2): ##STR36## wherein X is one or more radicals selected from the group consisting of a direct bond, divalent hydrocarbon radical having 1˜10 carbon atoms, hexafluorinated isopropylidene, carbonyl, thio, sulfonyl and ether radical, and Y1, Y2, Y3 and Y4 are individually one or more radicals selected from the group consisting of a halogen atom, lower alkyl radical, lower alkoxy radical, chlorine atom and bromine atom; and R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4˜9 carbon atoms, monocyclic aliphatic radical having 4˜10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member and wherein the polyimide is different from the polyetherimide.
3. A polyimide based resin composition comprising 1˜50 parts by weight of polyetherimide for 100 parts by weight of a resin composition comprised of 50˜1 parts by weight of polyarylether ketone and 50˜99 parts by weight of a polyimide having recurring structural units represented by the formula (3): ##STR37## wherein R is a tetravalent radical selected from the group consisting of an aliphatic radical having 4˜9 carbon atoms, monocyclic aliphatic radical having 4˜10 carbon atoms, monoaromatic radical, condensed polyaromatic radical, and noncondensed aromatic radical connected to each other with a direct bond or a bridge member and wherein the polyimide is different from the polyetherimide.
4. A polyimide based resin composition of claim 1, 2 or 3 wherein the amount of the polyetherimide is 5˜25 parts by weight for 100 parts of the resin composition comprising polyimide and polyarylether ketone.
5. A polyimide based resin composition of claim 1, 2 or 3 wherein the amount of the polyetherimide is 10˜20 parts by weight for 100 parts of the resin composition comprising polyimide and polyarylether ketone.
6. A polyimide based resin composition of claim 1, 2 or 3 wherein the polyimide comprises an end-capped polymer obtained by preparing said polyimide in the presence of aromatic anhydride represented by the formula (4): ##STR38## wherein Z is a divalent radical having 6˜15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member, and/or aromatic monoamine represented by the formula (5):
V--NH.sub.2                                                ( 5)
wherein V is a monovalent radical having 6˜15 carbon atoms and being selected from the group consisting of a monoaromatic radical, condensed polyaromatic radical and noncondensed aromatic radical connected to each other with a direct bond or a bridge member.
7. A polyimide based resin composition of claim 1, 2 or 3 wherein the polyarylether ketone has a least one recurring structural unit selected from the group consisting of from formula (6) to formula (10): ##STR39##
8. A polyimide based resin composition of claim 1, 2 or 3 wherein the polyetherimide has a recurring structural unit represented by the formula (11): ##STR40##
9. A polyimide based resin composition of claim 1, 2 or 3 wherein the composition is improved their permanence properties by heat treating at temperature of from 150° C. to 370° C.
10. A polyimide based resin composition comprises 5 to 65 parts by weight of fibrous reinforcements for 100 parts by weight of the polyimide based resin composition of claim 1, 2 or 3.
11. An injection molded article obtained from the polyimide based resin composition of claim 1, 2 or 3.
US08/297,854 1993-09-01 1994-08-30 Polyimide based resin composition Expired - Fee Related US5473010A (en)

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US6115514A (en) * 1993-05-07 2000-09-05 Nippon Telegraph And Telephone Corporation Optical waveplate, method of manufacturing the same, and waveguide device using the same
US6232428B1 (en) * 1999-01-19 2001-05-15 I.S.T. Corporation Essentially colorless, transparent polyimide coatings and films
US20030091827A1 (en) * 2001-09-28 2003-05-15 Zamora Paul O. Plasma cross-linked hydrophilic coating
US20070066737A1 (en) * 2005-09-16 2007-03-22 Gallucci Robert R Flame retardant polymer blends
US20070066765A1 (en) * 2005-09-16 2007-03-22 General Electric Company Polyarlyl ether ketone polymer blends
US20090292362A1 (en) * 2008-05-20 2009-11-26 Warsaw Orthopedic, Inc. Intervertebral implant and methods of implantation and manufacture
US20100151173A1 (en) * 2007-04-27 2010-06-17 Nicolangelo Peduto Polyamide materials having high fluid barrier properties
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6115514A (en) * 1993-05-07 2000-09-05 Nippon Telegraph And Telephone Corporation Optical waveplate, method of manufacturing the same, and waveguide device using the same
US6232428B1 (en) * 1999-01-19 2001-05-15 I.S.T. Corporation Essentially colorless, transparent polyimide coatings and films
US20030091827A1 (en) * 2001-09-28 2003-05-15 Zamora Paul O. Plasma cross-linked hydrophilic coating
US20070066737A1 (en) * 2005-09-16 2007-03-22 Gallucci Robert R Flame retardant polymer blends
US20070066765A1 (en) * 2005-09-16 2007-03-22 General Electric Company Polyarlyl ether ketone polymer blends
US20070219324A1 (en) * 2005-09-16 2007-09-20 Ashish Aneja Poly aryl ether ketone polymer blends
US9006348B2 (en) 2005-09-16 2015-04-14 Sabic Global Technologies B.V. Poly aryl ether ketone polymer blends
US9011998B2 (en) * 2005-09-16 2015-04-21 Sabic Global Technologies B.V. Polyaryl ether ketone polymer blends
US20100151173A1 (en) * 2007-04-27 2010-06-17 Nicolangelo Peduto Polyamide materials having high fluid barrier properties
US20090292362A1 (en) * 2008-05-20 2009-11-26 Warsaw Orthopedic, Inc. Intervertebral implant and methods of implantation and manufacture
US8518113B2 (en) 2008-05-20 2013-08-27 Warsaw Othopedic, Inc. Intervertebral implant and methods of implantation and manufacture
US9400091B2 (en) 2008-12-19 2016-07-26 Sabic Global Technologies B.V. Moisture resistant polyimide compositions

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